5-arylazo-pyrimidine monoazo dyestuffs

ABSTRACT

1,188,610. Mono- and dis-azo dyestuffs. J. R. GEIGY A.G. 26 April, 1968 [28 April, 1967], No. 19864/68. Addition to 1,109,628. Heading C4P. The invention comprises dyestuffs containing no ionic groups forming salts in water and having the general formula wherein A is a carbocyclic or heterocyclic aromatic radical which may contain an arylazo group, one of X 1 , X 1  and X 3  is -O-, -S- or -NH- and each other X is -NH-, at least one of R 1 , R 2  and R 3  is a radical -alk -O-Z wherein alk is an optionally substituted alkylene radical and Z is H, an acyl radical or an optionally substituted hydrocarbon radical and the other R&#39;s each represent an optionally substituted alkyl, cycloalkyl, or aralkyl group or a phenyl radical bound by -O- or -S- to the pyrimidine nucleus. Preferably A is a phenyl radical having a nitro group in the o- and/or pposition to the azo link which may be further substituted or a benzthiazolyl-(2)- radical optionally substituted by chlorine, bromine, nitro, cyano, thiocyano, alkyl, alkoxy or alkylsulphonyl. Other values of A specified include naphthalene, pyrazole, thiazole, oxadiazole, thiodiazole, triazole, pyridine, benzothiazole, indazole or quinoline. They are prepared by diazotization and coupling or by acylation of the corresponding compound where at least one R 1 , R 2  and R 3  is -alk-OH. Coupling may take place in presence of methanol, D.M.F., ethylene glycol monoethylether or cetyl or oleyl polyglycol ethers. The dyestuffs give yellow, orange, red and brown shades on hydrophobic organic textile fibres e.g. polyesters, cellulose 2¢ and triacetates.

United States Patent Ofice 3,531,457 Patented Sept. 29, 1970 US. Cl.260154 Claims ABSTRACT OF THE DISCLOSURE Dispersible dyes which are 5arylazopyrimidines wherein one of the carbon atoms in 2-, 4- and6-position of the pyrimidine ring is substituted by an aliphatic,araliphatic, cycloaliphatic or carbocyclic aromatic radical bound by wayof an -O or -S--- bridge to the pyrimidine nucleus and the remainingcarbon atoms in the'aforesaid positions are substituted byaliphatically, araliphatically or cycloaliphatically mono-substitutedamino groups and the arylazo moiety comprises preferably a nitrophenylradical; such dyestuffs being distinguished by good aflinity especiallyfor polyester fibers, affording dyeings on these fibers which have goodfastness properties and especially good light fastness; processes fordyeing polyester fibers with the aforesaid dyestuffs; and compositionscontaining polyester fiber materials and such dyestuffs.

DESCRIPTION OF THE INVENTION The present invention concerns new,difficultly water soluble dyestuffs which can be used as dispersiondyestuffs, processes for their production, processes for the dyeing ofhydrophobic organic fiber material, particularly textile fibers madefrom linear high molecular esters of aromatic polycarboxylic acids withpolyvalent alcohols or from cellulose esters and, as industrial product,the fiber material dyed with the new dyestuffs.

It is common knowledge that a prerequisite for the successful dyeing ofpolyester fibersin addition to satisfactory fastness properties both onapplication and in use-is an excellent drawing power and unexpectedlygood buildup of the dispersion dyestuffs used therefor. However, thedyeing of texturized polyester fiber material, i.e. fabrics made fromcrimp yarn, e.g. Crimplene, makes great demands of the dyestuffs to beused since, for this purpose, in addition to good fastness propertiesand sufficient drawing power and buildup, very good leveling power ofthe dyestuffs is imperative.

It has now been found that new, dif'ficultly water soluble dyestuffswhich meet the above and other requirements conventionally made ofdispersible dyes, are those of the formula wherein A, represents aphenyl radical substituted as follows:

(a) by, as first substituent, a nitro group;

(b) by a second substituent selected from nitrogen, nitro, cyano,chlorine, bromine, lower alkyl, lower alkoxy, phenoxy, loweralkylsulfonyl, phenoxysulfonyl, lower alkylphenoxysulfonyl, loweralkoxycarbonyl, hydroxy lower alkoxycarbonyl, lower alkoxy-loweralkoxycarbonyl and a substituent of the formula wherein Q represents SOor CO-;

R represents hydrogen, lower alkyl, hydroxy-lower alkyl, loweralkoxy-lower alkyl, benzyl or cyclohexyl; and

R represents hydrogen, lower alkyl or hydroxyl-lower alkyl; and

(c) by a third substituent selected from hydrogen, chlorine or bromine;

One of the groupings -R R and R represents alkyl of from 2 to 5 carbonatoms substituted by at least one of the following; hydroxy, loweralkoxy, cyclohexyloxy, benzyloxy, a phenyloxy radical any substituent ofwhich is selected from hydrogen, lower alkyl, lower alkoxy, chlorine andbromine; lower alkanoyloxy, benzoyloxy, lower alkoxy-carbonyloxy,phenyl-sulfonyloxy and lower alkyl-phenyl-sulfonyloxy; and

Each of the remaining (R')s represents lower alkyl, cyclohexyl, benzyl,hydroxy-lower alkyl, lower alkoxylower alkyl or lower alkanoyloxy-loweralkyl, or a phenyl radical bound by way of an -O or S bridge to thepyrimidine nucleus, and

One of X X and X represents O or S, and the other tWo Xs represent NH-.

Preferably the aforesaid nitro substituent of A is in 0- or p-positionrelative to the azo bridge at the said phenyl radical.

The dyestuffs according to the invention which fall under Formula IIIAare suitable mainly for the dyeing of hydrophobic, organic fibermaterial from aqueous dispersion, in particular for the dyeing oftextile fibers made from linear high molecular esters of aromaticpolycarboxylic acids with polyfunctional alcohols, e.g. made frompolyglycol terephthalates, polyglycol isophthalates or polycyclohexanediol terephthalates, or made from cellulose esters, e.g. cellu1ose-2/2-acetate and cellulose triacetate fibers they produce strongly coloredgreenish yellow, yellow, orange, scarlet, red and brown dyeings whichhave excellent fastness to washing, milling, sublimination, light,rubbing, perspiration, solvents, crossdyeing, decatising, gas fading andindustrial fumes.

Dyestuffs according to the invention can also be used, however, for thedyeing of synthetic polyamide fibers such as nylon, as well as for thedyeing of polyolefins, particularly polypropylene fibers.

Polyglycol terephthalate fibers are dyed with aqueous dispersions ofdyestuffs according to the invention preferan ably at temperatures ofover 100 C. under pressure. The dyeing can also be performed at theboiling point of the dye liquor however, in the presence of carrierssuch as alkali metal phenyl phenolates, polychlorobenzene compounds orsimilar auxiliaries, or it can be performed by the pad-dyeing processfollowed by a heat treatment, e.g., thermofixing at l80220 C.Cellulose-2 /2-acetate fibers are preferably dyed at temperatures of80-85 C. whilst cellulose triacetate fibers and synthetic polyamidefiber material are advantageously dyed at the boiling point of thedyebath. The use of carriers is not necessary When dyeing the lastmentioned type of fibers. Azo dyestuffs according to the invention canalso be used for printing the materials mentioned by the usual methods.

In addition, vegetable and animal fibers, particularly cotton or wool,are very well reserved by the dyestuffs according to the invention. Evenon tightly woven fabric or tightly twisted yarns, good and level,penetrated dyeings are obtained with the dyestuffs according to theinvention.

Dyestuffs according to the invention, particularly as mixtures ofisomers, differ from previously known dyestuffs of similar constitutionby their good drawing power and buildup onto polyglycol terephthalatefibers. In addition, in most cases, dyeings attained with dyestuffsaccording to the invention have substantially better fastness to lightand sublimation.

Dyestuffs according to the invention are also suited for the dyeing ofcellulose acetates, polyglycol terephthalates and polyamides in themass. Because of their good solubility in organic solvents such asacetone or chloroform, they can also be used in lacquers and printinginks.

The azo dyestuffs of Formula IIIA and dyestuffs of similar structure butsome of which are less easily producible, and which are generally ofinferior light fastuess are obtained by coupling the diazonium compoundof an I amine of the formula ANH (I) with a coupling component of theformula XiR1 N X2R2 m XsRa (u) to form an azo dyestull of the formula Xrli N AN:N- X::ltz

m xt1ta (1 I I) In this coupling, the starting materials should be sochosen that the azo dyestuff obtained contains no ionogenic groupsforming salts in water, i.e., it contains neither groups whichdissociate acid in water such as sulfonic acid, carboxylic acid orphosphoric acid groups, nor onium groups such as ammonium or sulfoniumgroups.

In the Formulas I, II and III:

A represents a carbocyclic or heterocyclic aryl radical,

of X X and X one X represents an O or S bridge and the two other Xs eachrepresent an NH bridge, and

of R R and R at least one R represents a radical of the formula alkO-Zwherein -alkreprcsents 41 an optionally substituted alkylene radical andZ represents hydrogen, an acyl radical or an optionally substitutedhydrocarbon radical, and the other Rs each represent an optionallysubstituted alkyl, cycloalkyl or aralkyl group.

When A is a carbocyclic aryl radical, then this is a monoorpoly-nuclear, condensed or non-condensed, particularly an unsubstitutedor non-ionogenically substituted phenyl or naphthyl radical. PreferablyA is a phenyl radical non-ionogenically substituted by electronattracting substituents. Examples of electron attracting, non-ionogenicsubstituents are: halogens such as fluorine, chlorine or bromine; thecyano, thiocyano, nitro, trifluoromethyl group; also acyl groups,particularly carbacyl groups such as low alkanoyl or alkenoyl groups,further the aroyl groups such as the benzoyl group, or organosulfonylgroups such as low alkylsulfonyl or arylsulfonyl groups, also sulfonicacid aryl ester groups such as the sulfonic acid phenyl ester,alkylphenyl ester or halogenophenyl ester groups; carboxylic acid estergroups, e.g., the carbophenoxy group, particularly however, carbalkoxygroups such as the carbomethoxy, carboethoxy, carboisopropoxy orcarbobutoxy group; the sulfonic acid or carboxylic acid amide group;N-monoor N,N-disubstituted carbamoyl or sulfamoyl groups having a phenylgroup and/ or alkyl, hydroxyalkyl, acyloxyalkyl substituents,particularly low alkanoyloxyalkyl, alkoxyalkyl, cyanoalkyl or cycloalkylor phenylalkyl substituents. All these groups can aso be furthersubstituted non-ionogenically. However, in addition to the preferred,electron attracting substituents, the radical A can also containnon-ionogenic electron repelling substituents, e.g., low aliphatic,optionally nonionogenically substituted, e.g., hydroxy substituted,hydrocarbon groups, optionally non-ionogenically substituted low alkoxygroups such as methoxy, ethoxy or ethoxycarbonylmethoxy groups,optionally non-ionogenically substituted aryloxy groups such as thephenoxy group and the alkyl or halogen substituted pheuoxy groups, oracylamino groups, particularly carbacylamino groups, e.g., lowalkanoylamino groups such as the acetylamino, aroylamino group such asthe benzoylamino group, or also low alkylsulfonylamino groups such asthe methylsulfonylamino group, or arylsulfonylamino groups such as thephenylsulfonylamino group.

When A is a naphthyl radical, it can be both an unsubstituted as well asa non-ionogenically substituted 1- or Z-naphthyl radical. Substituentsin this case are mainly low alkyl and alkoxy groups, halogens such aschlorine or bromine, optionally N-substituted sulfonic acid amidegroups, sulfonic acid low alkyl ester or low aryl ester groups, lowalkylsulfonyl or arylsulfonyl groups.

When A contains an arylazo group, the azo groups in an aromatichomocycle preferably are in the p-position. The arylazo group ispreferably unsubstituted; however, it can also be substituted byhalogens such as fluorine, chlorine or bromine, or by low alkyl, lowalkoxy groups or by the nitro group. These substituents are ringsubstituents. If A is e.g. a phenylazophenyl radical, then the phenyleneradical can also contain further substituents, e.g. low alkyl or alkoxygroups, halogens such as fluorine, chlorine or bromine, or acylaminogroups such as low alkanoylamino groups.

When A is a heterocyclic aryl radical then it is mainly radicals of 5-or 6-membered, particularly N-containing, heterocycles of, e.g. thepyrazole, thiazole, oxidiazole, thiodiazole, triazole or pyridineseries. It can also be radicals of mononuclear condensed heterocycleswhich then, preferably, have a fused benzene ring, such as optionallynon-ionogenically substituted. benzothiazole, indazole or quinolinerings. These monoor poly-nuclear heterocyclic aryl radicals can alsocontain non-ionogenic substituents of the type listed above which areusual in azo dyestuffs, particularly halogens, pseudohalogens such ascyano or thiocyano groups, nitro groups, lower alkyl,

lower alkoxy, phenyl groups, lower alkylsulfonyl groups and sulfonicacid amide groups optionally substituted by lower alkyl or dialkylgroups.

Preferred azo dyestuffs according to the invention are those fallingunder Formula IIIA which are produced by using diazonium compounds ofamines of Formula I wherein A represents a phenyl radical having a nitrogroup in and/or p-position to the azo group, which phenyl radical isoptionally substituted by other nonionogenic, preferably electronattracting substituents.

In order to attain the desired sublimation fastness properties and avery good levelling power and buildup, at least one R in the azodyestuffs of Formula III according to the invention must be thecharacteristic group alkOZ. The alkylene group alk can be straight orbranched chained; in the former case it is preferably the 1,2-ethyleneor 1,3-propylene group, in the latter case it is the 1,2-propylene or1,2-butylene group. Such divalent radicals can be substituted, e.g. byphenyl or lower alkoxy groups such as the methoxy or ethoxy group.

As acyl radical, Z is particularly a lower, unsubstituted ornon-ionogenically substituted alkanoyl group the alkanoyl moiety ofwhich preferably has 2 to 4 carbon atoms. As nonionogenic substituents,the alkanoyl group can contain, e.g. halogens such as chlorine orbromine, or low alkoxy groups such as the methoxy or ethoxy group.

As hydrocarbon radical, Z represents, e.g. a straight or branched chainalkyl radical having, preferably, 1 to 4 carbon atoms, a cycloalkylradical such as the cyclohexyl or methylcyclohexyl radical, an aralkylradical, particularly a phenylalkyl radical such as the benzyl radical,or a homocyclic aryl radical such as the phenyl radical. When thesehydrocarbon radicals are substituted, then examples of substituents arehalogens such as fluorine, chlorine or bromine, cyano groups, phenylgroups, hydroxyl groups, low alkoxy groups or phenoxy groups.Preferably, however, Z is hydrogen.

When each of R R and R represents an alkyl radical then this can have upto 12, preferably 1 to 5 carbon atoms and the chain can be straight orbranched. If this alkyl radical is substituted, examples of substituentsare the hydroxyl group, alkoxy groups such as unsubstituted alkoxy,alkoxyalkoxy or alkoxyalkoxyalkoxy groups or alkoxycarbonyl groups, ineach of which the alkoxy unit preferably has 1 to 4 carbon atoms, alsoacyloxy groups, particularly low alkanoyloxy groups such as theacetyloxy or propionyloxy group, phenyl groups, phenoxy groups cyanogroups or halogens such as fluorine, chlorine or bromine. Cycloalkyl oraralkyl radicals symbolised by R R and R are, e.g. the cyclohexyl ormethyl-cyclohexyl groups or phenyl alkyl groups such as the benzylgroup, the benzene nuclei of which can contain the nonionogenicsubstituents, particularly low alkyl or alkoxy groups, listed above forA.

The pyrimidine compounds of Formula II usable as coupling componentsaccording to the invention are produced by reacting the three chlorineatoms of the 2,4,6- trichloro-pyrimidine one after the other withprimary aliphatic, cycloaliphatic or araliphatic amines as defined orwith a metal salt of an aliphatic, cycloaliphatic or araliphatichydroxyl or mercapto compound as defined. Preferably, less reactiveamines are used in the first step, and, in the second and third steps,more easily reactive, more strongly basic amines, alcoholates ormercaptides are used in any order desired. The products resulting fromthe first step are generally mixtures of isorners of2-amino-4,6-dichloro-pyrimidines and 4-amino- 2,6-dichloro-pyrimidineswhich can be separated, if desired, by recrystallisation or bychromatographic adsorption, e.g. on aluminum oxide.

Preferably, however, the mixtures of isomers are used as they yieldmixtures of azo pyrimidine dyestuffs according to the invention whichare distinguished by unexpectedly good buildup.

The step-wise reaction is performed, e.g. in aqueous, organic ororganic-aqueous solution or dispersion, optionally in the presence ofacid binding agents such as alkali and alkaline earth carbonates oroxides, or tertiary nitrogen bases. Suitable organic solvents are, e.g.alcohols such as methanol or ethanol, ethylene glycol monomethyl etheror monoethyl ether, preferably however, aliphatic ketones such asacetone, methylethyl ketone or methylisobutyl ketone, cyclic ethers,e.g. dioXane and tetrahydrofuran, or optionally halogenated or nitratedaromatic hydrocarbons such as toluene, xylenes, chlorobenzene ornitrobenzene.

The reaction of the first chlorine atom of the 2,4,6-trichloro-pyrimidine is performed at low temperatures, advantageously at2060 C., the second chlorine atom is reacted at moderate temperatures,preferably at l00 C., and the third chlorine atom is reacted at highertemperatures, preferably between and C., optionally in a closed reactionvessel.

If, in the pyrimidine coupling components of Formula II usable accordingto the invention, one R of R R and R represents a radical of the formulaalkOI-I and the other Rs each represent an alkyl radical containing, asnon-ionogenic groups, optionally one or more hydroxyl groups, then thesehydroxyl groups can be subsequently acylated. Acylating agents for thispurpose are the anhydridcs or low carboxylic acids such as aceticanhydride or propionic acid anhydride, acyl chlorides and bromides ofthe aliphatic and aromatic series, e.g. acetyl chloride, propionylchloride or benzoyl chloride or bromide, also chloroformic orbromoformic acid esters, particularly chloroformic or bromoformic acidmethyl or ethyl ester.

The diazonium compound of an amine of Formula I is coupled with thecoupling component of Formula II by the usual methods, preferably inmineral acid to weakly acid aqueous medium, in particular at a pH valueof 44.5. When the coupling is performed in a mineral acid medium,advantageously the acid is gradually buffered, e.g. with alkali metalsalts of low fatty acids. In many cases, the coupling of a mixture ofisomers of pyrimidine coupling components usable according to theinvention in particular with a suitable dia'zonium compound has provedto be very advantageous.

A modification of the process according to the invention for theproduction of difficultly water soluble azo dyestuffs of Formula IIIwherein of R R and R at least one R represents an alkyl radicalsubstituted by acyloxy groups, consists in reacting a compound of theformula Xa-Ra rv wherein A represents preferably A of R R and R one R"represents a radical of the formula alkOH and the other (R)s representthe aforesaid radical or an unsubstituted alkyl group, a substitutedalkyl group different therefrom or an optionally substituted cycloalkylor aralkyl group, and

X X X and alk have the meanings given above,

with an acylating agent, the starting materials being so chosen that theend dyestulf contains no ionogenic groups forming salts in water.

Azo compounds of Formula IV are obtained, e.g. by coupling the diazoniumcompound of an amine of For- 7 mula I with the corresponding pyrimidinecoupling component, the coupling being performed in the manner describedabove.

Suitable acylating agents for the acylating of azo compounds of FormulaIV usable according to the invention in the presence of a carrier suchas trichlorobenzene. The dyeings are very fast to light and sublimation.

The 2,4-bis-ethylamino-6-(3-hydroxy-ethoxy) pyrimidine used in thisexample as coupling component is obtained, e.g. by reacting the2,4-bis-ethylamino-6-chloroare, e.g. those mentioned above. 5 pyrimidinewith the monosodium salt of ethylene glycol The acylation is performedadvantageously at a raised at a temperature of 75-1-00. temperature in asuitable organic solvent such as glacial Dyestuffs having similar goodproperties are obtained acetic acid, chlorobenzene or dioxane,optionally in the when the equivalent amount of each of the diazocompresence of an acid binding agent such as sodium ace- 10 ponentsgiven in column 2 of the following Table I is tate or pyridine. coupledwith one of the coupling components given in The dyestuffs according tothe invention are brought column 3 under the conditions described inthis example.

TABLE 1 Example Shade on polyglycol No. Dlazo component Couplingcomponent terephthalate fibres 2 l-amino-4nitrobenzene2-(fl-hydroxy-ethylamino)-4-ethylamino-fi-plienoxy-pyrimidine Yellowishorange. 3, 1-amino-2-br0mo4-nitrob0nzene2-ethylamino-4-(-y-hydroxy-propylami110)-6-ethoxy-pyrimidine R (1130.

e ish orange.

l-amino-Z-methoxy-4-nitrobenzene 2,4-bis-ethylamino-6-(dmethoxyethoxy)-pyrimidine2,4-bis-methyla1nino-6-(fi-phenoxy-ethoxy)-pyrirnidine Orange.

5 l-arnino-Z-methyl-4-nitrobenzene 6 1-aniino-2,4-diniti'obenzene2-ethylamin0-4-(-y-mcthoxy-propylamino)-6-phenylthiopyrimidine Scarlet.7 do 2-ethy1amiu0-4-(,B-phenoxy-ethylamino)-6-butylthiopy1imidine Do. 8l-amino-Z,4-dinitrooclilorobenzene 2,4bis-ethylamino-fi-(fi-hydroxy-ethoxy)pyrimidine Orange.

into a finely distributed form by milling with surface active dispersingagents. Suitable dispersing agents are, e.g. anionic ones such as alkalimetal salts of sec. higher al kylaryl sulphonates, alkali metal salts ofcondensation products of formaldehydye with naphthalene sulphonic acids,lignin sulphonates, or non-ionogenic dispersing agents such as fattyalcohol polyglycol others.

In this specification and the appended claims the term lower (or low)used in connection with aliphatic radicals means groups containing notmore than 5 carbon atoms.

The following non-limitative examples illustrate the invention further.The temperatures are given therein in degrees centigrade and parts andpercentages are given by weight unless expressly stated otherwise.Polyglycol terephthalate represents the products known under the tradenames Terylene, Vycron, Dacron and Trevira.

EXAMPLE 1 16.3 g. of l-amin-ZFcyano-fl-nitrObenZene are dissolved in 200g. of concentrated sulphuric acid and, at 10, the solution is diazotizedwith an amount of nitrosyl sulphuric acid corresponding to 6.1 g. ofsodium nitrite. The diazonium salt solution so obtained is addeddropwise, at 0-5 to a solution of 22.6 g. of 2,4-bis-ethylamino-6-(fl-hydroxy-ethoxy)-pyrimidine in 100 g. of methyl alcohol, 150g. of 36% hydrochloric acid and 400 g. of water. The coupling mixture isstirred for 4 hours at 0l0. Then the precipitated dyestuff thecomposition of which corresponds to the formula is separated byfiltration, washed with water and then dried in the usual way. 10 g. ofthe dyestuff produced in this Way are brought into a finely dispersibleform by milling with g. of a lignin sulphonate. Polyglycol terephthalatefibres can be dyed in pure orange shades with this dye preparation fromaqueous dispersion, optionally By repeating Example 1, but using in lieuof the 1- amino-2-cyano-4-nitrobenzene employed therein an equivalentamount of an amine of the formula wherein Q Q and Q represent thesubstituents given in the respectively entitled columns of the followingTable II, and in lieu of the pyrimidine coupling component used thereinan equivalent amount of a coupling component of the formula wherein Y Yand Y have the meanings given in the respectively headed columns ofTable II, there are obtained the correspondingly substituted dyestuffsof the formula N 5:; Ya

which dye polyglycol terephthalate fibers in the shades given in thelast column of Table II, the resulting dyeings having the fastnessproperties described hereinbefore.

The cyclohexyl radical is represented by l3 EXAMPLE 41 In an apparatusfor dyeing under pressure, 4 g. of the dyestuff obtained according toExample are finely suspended in 2000 g. of water which contains 4 g. ofoleyl polyglycol ether. The pH of the dyebath is adjusted to 55.5 withacetic acid.

100 g. of polyglycol terephthalate fabric are then introduced at 50, thebath is heated within minutes to 140 and dyeing is performed for 50minutes at this temperature. The dyeing is then rinsed with water,soaped and dried. Under these conditions, a pure orange dyeing isobtained which is fast to washing, perspiration, light and sublimation.

The dyestuffs described in the other examples produce dyeings of equalquality by this process.

EXAMPLE 42 2 g. of the dyestuff obtained according to Example 36 aredispersed in 4000 g. of water. 12 g. of sodiumophenylphenolate are addedto this dispersion as carrier and also 12 g. of diammonium phosphate areadded, and 100 g. of polyglycol terephthalate yarn are dyed for 1 /2hours at 95-98". The dyeing is rinsed and aftertreated with dilutesodium hydroxide solution and a dispersing agent.

In this way, a pure orange dyeing which is fast to washing, light andsublimation is obtained.

If in the above example, the 100 g. of polyglycol terephthalate yarn arereplaced by 100 g. of cellulose triacetate fabric, dyeing is performedunder the conditions given and then the dyeing is rinsed with water, anorange dyeing is obtained which has very good fastness to washing andsublimation.

EXAMPLE 43 Polyglycol terephthalate fabric is impregnated in a paddingmangle at 40 with a liquor of the following composition:

parts by weight of the dyestuff obtained according to Example 1, finelydispersed. in

7.5 parts by weight of sodium alginate,

20 parts by weight of triethanolamine,

20 parts by weight of octylphenol polyglycol ether and 900 parts byweight of water.

The fabric squeezed out of a content of about 100% impregnation liquoris dried at 100 and then is fixed for 30 seconds at a temperature of210. The dyed goods are rinsed with water, soaped and dried. Under theseconditions, an orange dyeing is obtained which is fast a to washing,rubbing, light and sublimation.

The dyestuffs described in the other examples produce dyeings of equalquality by this process.

EXAMPLE 44 2 g. of the dyestuif produced according to Example 9 aredispersed in 4000 g. of water. 8 g. of oleic acid-N- methyl tauride areadded to this dispersion and 100 g. of cellulose-2 /z-acetate yarn aredyed for 1 hour at 80. The dyeing is rinsed and then dried.

In this way, an orange dyeing is obtained which is fast to perspiration,rubbing and light.

A represents a phenyl radical substituted as follows:

(a) by, as first substituent, a nitro group; (b) by a second substituentselected from hydrogen, nitro, cyano, chlorine, bromine, lower alkyl,lower alkoxy, phenoxy, lower alkylsulfonyl, phenoxysulfonyl, loweralkylphenoxysulfonyl, lower alkoxycarbonyl, hydroxy-loweralkoxycarbonyl, lower alkoxy-lower alkoxycarbonyl and a substituent ofthe formula wherein 10 Qrepresents SO orCO;

R represents hydrogen, lower alkyl, hydroxy-lower alkyl, loweralkoxy-lower alkyl, phenyl, benzyl or cyclohexyl; and R representshydrogen, lower alkyl or hydroxy-lower 15 alkyl;and

(c) by a third substituent selected from hydrogen,

chlorine or bromine;

one of the radicals R R and R represents alkyl or phenyl alkyl the alkylgroup having from 2 to 5 carbon atoms substituted by one of thefollowing: hydroxy, lower alkoxy, cyclohexyloxy, benzyloxy, phenyloxy,phenyloxy substituted by a member of the group of (a) lower alkyl, (b)lower alkoxy, (c) chlorine and ,(d) bromine, lower alkanoyloxy,benzoyloxy, lower alkoxycarbonyloxy, phenyl-sulfonyloxy and loweralkylphenylsulfonyloxy;

a second R represents lower alkyl, cyclohexyl,

benzyl, hydroxy-lower alkyl, lower alkoxylower alkyl or loweralkanoyloxy-lower alkyl,

the third R represents the same group as the second R or a phenylradical bound by way of an -O or -S- bridge to the pyrimidine nucleus,and

one of X X and X represents O- or --S,

and the other two Xs represent NH.

2. A dyestuff as defined in claim 1, wherein said nitro groupsubstituent of A is in 0- or p-position relative to the axe bridge atthe said phenyl radical.

40 3. A dyestulf as defined in claim 2, which is of the formula ClNH-C2H5 N O2N N:N -N H- C 2H5 415 I N N02 OCH2CII2OH 4. A dyestuff asdefined in claim 2, which is a mixture of the two isomers falling underthe formula References Cited UNITED STATES PATENTS 7/1962 Lewis 260l54 XCHARLES B. PARKER, Primary Examiner D. M. PAPUGA, Assistant Examiner Us.c1. X.R.

